US3615455A - Photopolymerization of ethylenically unsaturated organic compounds - Google Patents

Photopolymerization of ethylenically unsaturated organic compounds Download PDF

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Publication number
US3615455A
US3615455A US779625A US3615455DA US3615455A US 3615455 A US3615455 A US 3615455A US 779625 A US779625 A US 779625A US 3615455D A US3615455D A US 3615455DA US 3615455 A US3615455 A US 3615455A
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photopolymerization initiator
ethylenically unsaturated
photopolymerization
bromine
unsaturated organic
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Urbain Leopold Laridon
Gerard Albert Delzenne
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Agfa Gevaert NV
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Agfa Gevaert NV
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G03F7/0295—Photolytic halogen compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
    • C08F291/18—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00 on to irradiated or oxidised macromolecules
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making
    • Y10S430/114—Initiator containing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making
    • Y10S430/114—Initiator containing
    • Y10S430/122—Sulfur compound containing
    • Y10S430/123—Sulfur in heterocyclic ring
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making
    • Y10S430/114—Initiator containing
    • Y10S430/126—Halogen compound containing

Definitions

  • Z represents chlorine or bromine
  • R represents hydrogen chlorine bromine or acetyloxy
  • R' and R" represent benzoyl, nitrobenzoyl, dimethylaminobenzoyl, phenylsulfonyl, carboxyphenylsulfonzl, methzlphenzlsulfonyl, or naphthoyl,
  • X and Y represent carbonxl or sulfonyl is described. Exposure times for the polymerization is substantially reduced permitting use of low-intensity radiation.
  • the present invention relates to the photopolymerization of ethylenicallyunsaturated organic compounds and to polymers obtained therefrom.
  • the photopolymerization of ethylenically unsaturated organic compounds can be initiated by exposure to high intensity radiation such as ultraviolet radiation. For instance, when exposing methyl acrylate, for a long time to sunlight, it is transformed into a transparent mass (cf. Ellis: The Chemistry of Synthetic Resins, Vol. II (1935) page 1072).
  • high intensity radiation such as ultraviolet radiation.
  • methyl acrylate for a long time to sunlight, it is transformed into a transparent mass (cf. Ellis: The Chemistry of Synthetic Resins, Vol. II (1935) page 1072).
  • polymerization by the use of mere light proceeds at a much slower rate as compared with polymerization brought about by a free radical-generating catalyst or by heat.
  • the low rate of polymerization necessitates the use of extremely intense radiations, such as those obtained from high intensity carbon arcs.
  • a process for the photopolymerization of ethylenically unsaturated organic compounds comprises irradiating with light of wavelengths ranging from 2,500 to 5,000 Angstroms a composition comprising a photopolymerizable ethylenically unsaturated organic compound and as a photopolymerization initiator a diacylhalomethane corresponding to one of the following general Formulas:
  • halogen represents a halogen atom such as chlorine and bromine
  • R represents a hydrogen atom, a chlorine or a bromine atom, or an acetyloxy group
  • R and R" represents a benzoyl group, a nitro-benzoyl group, a dimethylamino benzoyl group, a phenyl-sulphonyl group, a carboxyphenylsulphonyl group, a methyl-phenyl-sulphonyl group, or a naphthoyl group,
  • X and Y represent a carbonyl group or a sulphonyl group.
  • diacylhalomethanes are obtained by halogenation of the corresponding diacylmethanes in chloroform or in acetic acid.
  • diacylhalomethanes are: 2-bromol ,3-diphenyll ,3-propanedione 2,2-dibromo-1,3-diphenyl-l ,3-propanedione 2-bromo-2-hydroxy-l ,S-diphenyl-l ,3-propanedione, acetate 2-bromo-2-(phenylsulphonyl)-acetophenone 2,2-dibromo-2-(phenylsulphonyl)-acetophenone 2-bromo-2-(p-tolylsulphonyl)-acetophenone 2-bromo-2-(phenylsulphonyl)-4'-nitro-acetophenone 2-br0mo-2-( phenylsulphonyl)-4-dimethylaminoacetophenone 2bromo-2-(m-carboxyphenylsulphonyl) acetophenone 2-bromo-2-(phenyls)-2
  • the ethylenically unsaturated organic compounds may be exposed to any source of radiation providing wavelengths in the range of 2,5005,000 Angstroms, preferably in the wavelength region of 3,0004,000 Angstroms.
  • Suitable light sources include carbon arcs, mercury vapor lamps, fluorescent lamps, argon glow lamps, photographic flood lamps, and tungsten lamps.
  • ordinary daylight may also be used.
  • the photopolymerization can be carried out according to any of the well-known processes, such as bulk-, emulsion-, suspension-, and solution-polymerization processes. In all these processes, the addition of a diacylhalomethane according to the invention to polymerizable materials subjected to the action of actinic light greatly increases the rate of photopolymerization.
  • a base or support may be coated with a solution of the ethylenically unsaturated organic compound in a solvent therefore, this solution containing in dissolved state or homogeneously dispersed therein aphotopolymerization-initiating diacylhalomethane, whereupon the solvent or solvent mixture is eliminated by known means such as evaporation, leaving a more or less thin coating of the ethylenically unsaturated organic compound on the base or support. Thereafter the dried photopolymerizable coating is exposed to actinic light rays.
  • the polymerization When exposing the photopolymerizable composition to actinic light rays the polymerization does not start immediately. Only after a short period, which among others depends on the ethylenically unsaturated organic composition, the photopolymerization initiator, and the light intensity used, the photopolymerization starts.
  • the period necessary for obtaining a perceptible amount of polymerization is a measure of the efficiency of the photopolymerization initiator, and is named the inhibition period.
  • the photopolymerizable composition comprises a hydrophilic or hydrophobic colloid as carrier or binding agent for the ethylenically unsaturated organic compound and the photopolymerization-initiating diacylhalomethane.
  • this binding agent By the presence of this binding agent the properties of the light-sensitive layer are of course highly influenced.
  • the choice of the binding agent is dependent on its solubility in solvents, which can also be used as solvents for the ethylenically unsaturated organic compounds and for the diacylhalomethane of the invention.
  • binding agents are, e.g., polystyrene, polymethyl methacrylate, polyvinyl acetate, pdyvinylbutyral, partially saponified cellulose acetate and other polymers that are soluble in solvents for initiators and monomers.
  • water-soluble polymers can be used such as gelatin, casein, starch, carboxymethylcellulose and polyvinylalcohol.
  • the ratio of photopolymerizable composition to binding agent obviously also influences the photopolymerization. The larger this ratio, the higher the photopolymerization rate of one particular ethylenically unsaturated organic compound.
  • the photopolymerizable composition is water-soluble, water may be used as a solvent for coating the support. On the contrary, if water-soluble photopolymerizable compositions are used, organic solvents, mixtures of organic solvents, or mixtures of organic solvents and water may be employed.
  • compositions comprising ethylenically unsaturated organic compounds.
  • These compositions may comprise one or more ethylenically unsaturated polymerizable compounds such as styrene, acrylamide, methacrylamide, methyl methacrylate, diethylaminoethyl methacrylate, and acrylonitrile.
  • ethylenically unsaturated polymerizable compounds such as styrene, acrylamide, methacrylamide, methyl methacrylate, diethylaminoethyl methacrylate, and acrylonitrile.
  • the photopolymerizable composition may also comprise or 5
  • the following results were obtained. consist of unsaturated compounds having more than one car Exposure in dd in :5 by weigh. bon-to-carbon double bond, e.g. two terminal vinyl groups, or of p y of a polymeric compound being ethylenically unsaturated.
  • crossdinking 30 762 8.1 usually occurs by means of the plurally unsaturated compound.
  • compounds containing more than one :38 :22: carbon-to-carbon double bond are, e.g. 'divinylbenzene, 240 1604 diglycol diacrylates, and N,N-alkylene-bis-acrylamides.
  • polymeric compounds containing ethylenically unsatul 5 ration are, e.g., allyl esters of polyacrylic acid, maleic esters of EXAMPLE 2 olvinlalcoh h ro p y y 01 poly yd carbons yet contammg carbon
  • An amount of 10 ml. of acrylonitrlle in 10 ml. of benzene to-carbon double bonds, unsaturated polyesters, cellulose was brought in a borosilicate glass test tube together with 6.78 acetomaleates, and allylcellulose.
  • the products of the invention are useful as adhesives, coat- 0 ing and impregnating agents, safety glass-interlayers, etc.
  • photopolymerization of the compositions is carried out 28 1'23: :2: within a mold, optical articles such as lenses can be obtained.
  • the photopolymerizable compositions which contain dia- 30 180 2.700 33.9 cylhalomethanes are also useful in the preparation of photographic images and the present invention comprises spreading the polymerizable composition upon a surface such as a sur- EXAMPLE 3 face of metal and printing a design thereon photographically by exposure to light through a suitable image pattern.
  • a surface such as a sur- EXAMPLE 3 face of metal
  • the present invention comprises spreading the polymerizable composition upon a surface such as a sur- EXAMPLE 3 face of metal and printing a design thereon photographically by exposure to light through a suitable image pattern.
  • 35 An amount of l 4 of benzene; and the light induces polymerization in the exposed areas of the of f P y 'P P? was h t fl i ti composition whereby the polymeric brought in a borosrlicate glass test tube.
  • the dissolved oxygen layer is rendered insoluble in the solvent or solvents used for was removed as descnbed m example subseqflemly the applying the photopolymen'zable layer. Thereafter the nonexglass, tube was seale'i exposure sepafatlon of the posed areas are washed away with a solvent for the monomer- 40 Polymer fofmed were earned P as descnbed example ic material. In this way printing plates and photographic The followmg results were etching resists are manufactured, which can be further used as Exposure time in minutes Yield in mg. by weight planographic printing plates, as matrices for printing matter, as screens for silk screen printing, and as photoresists for etching.
  • the imagewise photopolymerization can also induce dif- 2g :2: ferential softening properties to the layer. This makes possible so 580 a reproduction process by material transfer when the imagewise photopolymerized layer is heated subsequently and so pressed against a receiving sheet, so that the softened areas E l 4 are transferred to the receiving sheet. 5
  • Test Initiator 1 2,2dibron1o-1,3diphenyi-1,3-propanedione 6 10 2... Z-bromo-l,3-dipheny1-1,3-propanedione 12 19 3.
  • 2-brorno-2-(phenyisulphonyl)-acetophenone 7 12 5.
  • 2,2-riibromo-benzolb -thiophene-3 (2H)one-1,1-dioxide 10 37 7 2-br0m0-2(m-carboxyphenylsulphonyl)-acetophenone 8 14 2,2-dibromo-1,3-indanedione 5 10 2-bromo-2-(p-tolylsulphonyl)-acetophenone 9 12 2-br0mo-2-(phenylsulphonyl)-4'-nitroacetophenone 6 14 2-bromo-2-(phenyisulphonyi) 4-dimethylamino-acetophenone.
  • EXAMPLE 5 An amount of 1X10 mole of dibromo-bis(phenylsulphonyl)-methane was dissolved in 4 ml. of ethylene glycol monomethyl ether. A solution of 3 g. of acrylamide in 5 ml. of water was added thereto. The resulting solution was brought in a borosilicate glass test tube and freed from dissolved oxygen by bubbling through nitrogen for 30 minutes. The test tube was then sealed and exposed to an 80-watt mercury vapor lamp placed at a distance of cm. A perceptible polymerization occurred after 30 minutes of exposure and after 70 minutes a yield of 90-95 percent was attained.
  • a fine image of the original was obtained after an exposure of min. when using 2-bromo-2-(phenylsulphonyl)- acetophenone or the acetate of 2-bromo-2-hydroxy'-l ,3- diphenyll ,3-propane-dione as initiator.
  • Process for the photopolymerization of ethylenically unsaturated organic compounds which comprises irradiating with light of wavelengths ranging from 2,500 to 500 Angstrom a composition comprising a photopolymerizable ethylenically unsaturated organic compound and as a photopolymerization initiator a diacylhalomethane corresponding to one of the following structural formulas:
  • Z represents chlorine or bromine
  • R represents hydrogen, chlorine, bromine or acetyloxy
  • R and R" represent benzoyl, nitrobenzoyl
  • X and Y represent carbonyl or sulfonyl.
  • the photopolymerization initiator is 2,2-dibromo-2-(phenylsulfo nyl)-acetophenone.
  • a process for the production of a polymeric photographic relief image which comprises irradiating to light of wavelengths ranging from 2,500 to 5,000 Angstrom through a master pattern a photographic element comprising a support having thereon a light-sensitive layer comprising at least one photopolymerizable ethylenically unsaturated organic compound and as a photopolymerization initiator a diacylhalomethane corresponding to one of the following structural formulas:
  • Z represents chlorine or bromine
  • R represents hydrogen, chlorine, bromine, or acetyloxy
  • R and R" represent benzoyl, nitrobenzoyl,
  • X and Y represent carbonyl or sulfonyl, whereby in the exposed areas said ethylenically-unsaturated organic compound is polymerized, and removing the layer in the nonexposed areas by washing with a solvent for said ethylenically unsaturated organic compound.
  • a photopolymerizable element comprising a support and superposed thereon a light-sensitive layer comprising at least one photopolymerizable organic compound and as photopolymerization initiator a compound containing a diacylhalomethane corresponding to one of the following structural formulas:
  • Z represents chlorine or bromine
  • R represents hydrogen, chlorine, bromine or acetyloxy
  • R and R" represent benzoyl, nitrobenzoyl,
  • X and Y represent carbonyl or sulfonyl.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US779625A 1968-01-12 1968-11-27 Photopolymerization of ethylenically unsaturated organic compounds Expired - Lifetime US3615455A (en)

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US3844790A (en) * 1972-06-02 1974-10-29 Du Pont Photopolymerizable compositions with improved resistance to oxygen inhibition
US3929490A (en) * 1974-03-28 1975-12-30 Sun Chemical Corp Photopolymeriziable compositions with polymeric initiators
US4048034A (en) * 1976-08-27 1977-09-13 Uop Inc. Photopolymerization using an alpha-aminoacetophenone
US4115224A (en) * 1972-04-21 1978-09-19 Akzo Nv Radiation acid curable resin compositions and process for curing them
US5217843A (en) * 1989-03-11 1993-06-08 Hoechst Aktiengesellschaft Positive radiation-sensitive mixture, and radiation-sensitive recording material produced therefrom for high-energy radiation
US5338641A (en) * 1989-09-09 1994-08-16 Hoechst Aktiengesellschaft Positive-working radiation-sensitive mixture and copying material produced therefrom comprising an α,α-bis(sulfonyl) diazo methane as an acid forming compound
US5340682A (en) * 1989-09-09 1994-08-23 Hoechst Aktiengesellschaft Positive-working radiation-sensitive mixture and copying material produced therefrom comprising an α-carbonyl-α-sulfonyl diazomethane, a water-insoluble binder and an acid cleavable compound
US5424166A (en) * 1990-02-28 1995-06-13 Hoechst Aktiengesellschaft Negative-working radiation-sensitive mixture containing diazomethane acid generator and a radiation-sensitive recording material produced therfrom
US5614351A (en) * 1989-03-11 1997-03-25 Hoechst Aktiengesellschaft Radiation-curable mixture, and radiation-sensitive recording material produced therefrom for high-energy radiation
WO2011062198A1 (ja) 2009-11-20 2011-05-26 富士フイルム株式会社 分散組成物及び感光性樹脂組成物、並びに固体撮像素子
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US20180079864A1 (en) * 2015-05-29 2018-03-22 Fujifilm Corporation Polyimide precursor composition, photosensitive resin composition, cured film, method for producing cured film, a semiconductor device, and method for producing polyimide precursor composition
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Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4115224A (en) * 1972-04-21 1978-09-19 Akzo Nv Radiation acid curable resin compositions and process for curing them
US3844790A (en) * 1972-06-02 1974-10-29 Du Pont Photopolymerizable compositions with improved resistance to oxygen inhibition
US3929490A (en) * 1974-03-28 1975-12-30 Sun Chemical Corp Photopolymeriziable compositions with polymeric initiators
US4048034A (en) * 1976-08-27 1977-09-13 Uop Inc. Photopolymerization using an alpha-aminoacetophenone
US5614351A (en) * 1989-03-11 1997-03-25 Hoechst Aktiengesellschaft Radiation-curable mixture, and radiation-sensitive recording material produced therefrom for high-energy radiation
US5217843A (en) * 1989-03-11 1993-06-08 Hoechst Aktiengesellschaft Positive radiation-sensitive mixture, and radiation-sensitive recording material produced therefrom for high-energy radiation
US5340682A (en) * 1989-09-09 1994-08-23 Hoechst Aktiengesellschaft Positive-working radiation-sensitive mixture and copying material produced therefrom comprising an α-carbonyl-α-sulfonyl diazomethane, a water-insoluble binder and an acid cleavable compound
US5338641A (en) * 1989-09-09 1994-08-16 Hoechst Aktiengesellschaft Positive-working radiation-sensitive mixture and copying material produced therefrom comprising an α,α-bis(sulfonyl) diazo methane as an acid forming compound
US5424166A (en) * 1990-02-28 1995-06-13 Hoechst Aktiengesellschaft Negative-working radiation-sensitive mixture containing diazomethane acid generator and a radiation-sensitive recording material produced therfrom
WO2011062198A1 (ja) 2009-11-20 2011-05-26 富士フイルム株式会社 分散組成物及び感光性樹脂組成物、並びに固体撮像素子
EP2390272A1 (en) 2010-05-31 2011-11-30 FUJIFILM Corporation Polymerizable composition, cured film, color filter, method of producing color filter and solid-state image sensor
EP2402818A1 (en) 2010-06-30 2012-01-04 FUJIFILM Corporation Photosensitive composition, pattern forming material, and photosensitive film, pattern forming method, pattern film, low refractive index film, optical device and solid-state imaging device each using the same
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